Process of purifying gases



Jan. 15,v 1929.

Filed April 17', 1926 WMP- ' A TTOHNEYS Patented Jan.'15, 1929.

UNITED STATI-:s PATENT/OFFICE.

JOSEPH a. DELY, E nunca, -NEw Yonx, AssIeNon 'ro A'rMos'PHEnIc NITROGEN concurren, or soEvAY, NEW Yonx, A conroaATIoN or NEW Yonx. A

rnocEss or PUEIFYING cAsEs.

Application med Api-11.17, i926. serial 110.102,741.

This invention relates more particularly to methods of purifying ammonia synthesis ases for example in al process of the type own as the de Jahn process. According to the de Jahn procedure,.a crude gas mix ture, whose major' ingredients are hydrogen, nitrogen,and CO, is subjected to catalytic treatment with steam under conditions which will result in a gas mixture containl0 ing hydrogen and nitrogen in a 3:1 ratio with C02, (carbon dioxide) CO, (carbon monoxide) and other substances inl admixture therewith and from now on regarded as impurities. .This gas mixture is subjected l5 to a pressure approximating 100 atmospheres and under that ressure the gas stream is purified and is nally in its puried state introduced into a catalytic con-- verter, wherein h'ydrogen and nitrogen combine to form ammonia, such ammonia being subsequently abstracted from the gases leaving the catalyst chamber or converter, while the remaining gases are returned to the system for further synthesis. The present invention is concerned with that phase of the de Jahn process which deals with the removal from the, gases in the pressure system of the ma'or part, that is substantially all2 of their 02 and CO impurities. The object of the invention is to deal with this phase of the operations more eiiciently and more economically than has heretofore been possible.

The process which is the subjectof the 85 present invention takes a course which is illustrated diagrammatically in the accompanying drawings in which Fig. 1 is a diaammatic illustration of the pressure purication system especially elaborated with 40 reference to the particulars involved in thev new process. Fig. 2 is a view of a character similar to Fig. 1, illustrating a modification of the resent invention and Fig. 3 shows a modigcation of a detail of Fig. 2.

In the drawings the line Z indicates a gas stream in which the nitrogen-h drogen gas in the 1 :3 relation, accom anied,- by' mr purities including CO, and O2 enter the compressor Y. The compressor Y ,subjects the ases to a pressure which may, for examp e, be approximately 100 atmospheres. The compressed gases enter the water scrubber U and pass out of the water scrubber through line E. -The water, `as itpasses through the scrubber U, removes from 'the gas b far the major portion of such CO2 as may e present in the gases and then discharges through a Pelton wheelV or e uivalentmeansXfor conserving'energy. 'T e as stream in E, now containing `asfimpuritles its lmtial CO impurit and alsol relatively small quantities of .gon is now paed through a causticsolution at ordinary temperature and then into the tower A or itmay [Siass directly into the scrubbing tower A. crubbmgllquor consistin vof a copper solut1on capable of absorbing O and preferably onslstmg of an ammomacal copper solution 1s introduced to the scrubbing tower throu h the line K. In case the gas stream to e puried is suiiiciently free from .CO2 impurlty not to require treatment for CO2 removal at this pomt the cop er\solution need not be ammomacal, althou'g an ammoniaeal solution is preferable in Aany event, When CO2 is` presentin the gas mixture the ammoniacal copper solution, because of its free ammonia content, absorbs CO2 and this absorption is favored b the fact that the copper-solution is intro uced into the tower A (Fig. 1) at about ordinary temperature. In the tower A, therefore, the larger part of the C()2 impurity which may be present in the gas stream in the line E is removed. Of course' the co per solution', being capable of absorbing C simultaneously removes in the tower A'a portionof the OO content of the gas. The gas mixture leaves the tower A through the line M and undergoes further purification. The' liquor leaving tower A passes through line^D into the regeneration system R and thencel into storage tanKS. From the storage supplyiil S a pressure puml P feeds va constant sup ly i of regenerate co per solution through lme K into the top o tower A. The nature of the copper solution vand of the steps employed'ln its regeneration are descrlbed in my Patent No. 1,597,345, issued August 24, 1926. Briefly stated, the regeneration consists in the expulsion from the spent liquor iowing through D, b means of heat, of'COz, and 00,. picked Vup y the liquor in its passage through tower'A, the cuprous-cupr1c condition of 'the liquorbeing rejuvenated by passing air through ,the liquor, and the a1`n-"` moniacal strength bein maintained bythe introduction into the liquor of the appropriate'amount of ammonia. lThe re en'P/ ra` tionsteps in thiscase involve theapp cation A110 modified b v H in which' the pressure pump P of heat, but not of refrigeration, at any tower A a temperature condition which a-pproximates the prevailing normal atmospheric temperature of the works in which the process pro eeds. The gases which leave the tower A 1g. 1) undergo a purification treatment which is identical with the treatment described in Vmy pending application hereinbefore identified. This treatment in'- volves introducing the gases into a tower B, which is being continuously supplied through the line. L with an ammoniacal copper`solution of the same kind as the solution used in tower A but refrigerated to a temperature approximating 0 C., for example.

low temperature condition of the liquor in tower B favors the desired removal of the CO from the gas. The spent liquor in tower B is circulated through line D and through a regenerator system R. If desired, a storage tank S may be used as a reservoir or this reservoir may be omitted. In either event, the regenerated solution from R is ,circulated by means of pressure pump P through the brine cooler F before the regenerated solution is permitted to enter the tower B through the line L. The foregoing treatment of the gases, first by a copper solution maintained at normal 'or moderate temperatures, followed by a treatment with a refrigerated copper solution of the same character, causes aurication which is relatively constant with reect to the minute quantities of CO and O2 impurities still lcarried in the gas stream leaving the system at O. The residual impurities in the gases leaving the system of Fig. 1 at maybe dea-lt with in a variety of ways, preferably in the manner described in my applicationI Serial No. 663,- 662, of September 19, 1923, and in the patent application filed Vby Fredrik. W. de' Jahn, Serial No. 638,451, filed May 12, 1923, an'd which need not be described at length .in this specication.

It is apparent that the process" thus far described with reference toJ Fig. 1 may-be combining the regeneration systems R, and R and S. In this case vthe ent liquor from tower A may flow, not t rough line D, but through the by-pass line N, be regenerated at R and stored in S and from S a part of the unrefrigerated solution will be withdrawn through the byass line ctions to establish the circulation through H, K, A, N, R, S. In the meantime such ofthe regenerated solution as is required for tower B is diverted at J and sent through its refrigerating system F. When the system is thus operated the line D and the regenerator and storage systems R, 'S may be regarded as emergency systems and may be entirely omitted.

Returning next to Fi shovm functions in sus 2, the system there tantially the saine manner as the system described with refersolution is introduced' through line L at the top ofthe tower T. It will be observed that in this instance the gases from E first come in contact with a copper solution at avmoderate temperature andthen, as the gases rise through tower T, they come in contact with the refrigerated copper solution, so that the evii'ect is that of scrubbing the gas stream with a copper solution first at a moderate temperature and subsequently at a refrigerated temperature. v The tower T may bedivided into two towers T and T as indicated in Fig. 3. This latter arrangement allows the originally refrigerated solution in '.lf (Fig. 3) ,to be withdrawn into that part of tower T wherein the solution approximates the condition of the spent solution' from T. The spent liquor in Fig. 2 passes through line D to the regeneration system R, thence to Storage` S, then through line G'r'to the branch J. At J a part of theA solution is diverted through line K in such a manner that the solution will enter tower T at a moderate or normal temperature. part of the regeneratedsolution is diverted through the brine cooler F and is then introduced through line L at approximately 0 C. into the top of the tower T.

It will be observed that in every case the major portion of the regenerated liquor is not caused to undergo refrigeration, but is led at' an unrefrierated temperature either to a separate scru hing tower or to a predetermined point in. a scrubbin tower into the top of which-refrigerated uor is fed, and that only a minor portion o the regenerated liquor is refrigerated.

At J another The procedure which constitutes the subject matter of this application presents important advantages over the process described in my Patent No. 1,597,345, issued August 24:, 1926. In the irstAplace there is the saving in refrigeration.

necessary to refrigerate only a part,` say about one-fourth. In the second place, the4 ccordiiig to thepres- 'Y ent process, instead of refrigerating the total volume, of circulating copper liquor, it is creased CO2 removal eiiciency, is to be found in its relation to the water scrubbing opra# tion at U. It has heretofore been customary to place the burden of removing substan-4 tially all of the CO2 of the gases, on the ``Water scrubber, which therefore requires a relatively large excess of water. According to the new process, the removal of these final fractions of CO2 may be imposed upon the copper liquor, so that the water scrubber is not re uired to perform any further function than t e removal of the more easily absorbed volumes of CO5. The copper system also functions as a safeguard against the variation in CO2 content of the exit gas from the' water scrubber, arising from incidental chan es in the operating conditions of the scrutier. Such changes may involve variations in the C()2 content and vlume of gas entering the scrubber, or changes inthe temperature and volume of the water entering the scrubber, decreasing or deficient activity in the cold caustic solution when used, or other variables. Such variations, more 0r less minor in degree, are all within the limits of the CO2 removal capacity of the copper solution, provided the pro er temperature conditions are observed. gy treating the gas mixture first with a solution at unrefrigerated temperature, a condition most favor-v able to the obsorption of CO2 is established. By then' following with the scrubbing of the gases by refrigerated liquor, conditions most favorable for the removal of the last portions of CO are established. The combined effect,

therefore, of scrubbing the pressure gases first with water, then with unrefrigerated copper solution, and finally with a refrigerated copper solution, is to bring about a more uniform and reliable method lof ridding the gases of their CO2 and CO impurities, while at the same time bringing about this important effect by oper/ating methods which represent economies over the lless efficient, methods thus far employed. When in the claims the phrase gascontaining an oxide of carbon impurity is employed, it is intended to refer thereby toa gas which coli'- tains admixed with it` as an impurity, CO or CO together with CO2.

I claim: v

1. The process of purifying a flowing gas containing an oxide of carbon impurity which comprises passing the gas. stream through three scrubbing stages, continuously introducing water to the first stage, continuously introducing ammoniacal. cuprous ,liquor at an unrefrigerated temperature to 'the' send stage, and continuously introducing ammoniacal cuprous liquor at a refrigerated temperature to the third stage 2. The process which comprises su jee-ting a .gas containing an oxide of, carbon impurity to water scrubbing, then scrubbin the resultant gas mixture with ammoniaca i prises scrubbing Athe gas with an ammoniacal copper solution having a lower temperature at lthe gasy outlet than at the gas inlet, regenerating the said solution, diverting a portion ofthe regenerated solution, introducin said diverted portion at a predetermine oint in the first' step for resuse, refrigerating the remaining portion of the regener.

ated solution, and returning said refri erated solution to a predetermined point 1n the first'step for re-use, said refrigerated solution being returned to a point further along in the first step than .that to which the diverted `solution is returned.

4. That improvement in the process of urifying gas containing an oxide of carbon impurity witlian ammoniacal copper solutionin a regenerativev system` which comprises divertin a major portion of the regenerated solution for direct use in scrubbing the gas,- scrubbing the gas therewith, refrigerating the minor. portion of said re-v generated solution and scrubbing the gas with the refrigerated portion of the solution following the step scrubbed withA the unrefri erated major. portion of the regenerated so ution.

5. The process o f purifying gases containingan oxide of carbon impurity which comin which the gas was copper liquor at approximately v'the revailprises scrubbing the gas with ammoniacal copper solution atA an unrefrigerated temperature and additionally scrubbing the gas with ammoniacal copper solution at a lower purifying a gas from CO by treatment with* copper liquor which coiiiprises scrubbing the gas at an lunrefrigerated temperature with y copper solution capable of absorbing CO and subsequently scrubbing the gas jat a refrigerated temperature with copper liquor` capable of absorbing CO.

7, In the process of purifying ya gas of CO by treatment with copper liquor preparatory to the use of said gas in ammonia synthesis conducted under elevated pressure, that m- 'prov'ement which comprises scrubbing the gas under substantially the same elevated pressure at which the subsequenty ammonia synthesis is conducted, with copper solution capable of absorbing ICO, at an. unrefrigerated temperature,- and subsequently, under the same pressure, scrubbing the'gas with 5 copper solution capable of absorbing CO, at

a refrigerated temperature.

8. The process which comprises preparing a gas mixture for use in ammonia synthesis,

sald mixture containing nitrogen and hy- 10 drogen as synthesis gases and CO as an impuriiy, 'and urifying said gas mixture of CO by scrub ing the gas mixture with copper solution capable ofA absorbing CO, at an unrefrigerated temperature, and subsequently scrubbing the thus scrubbed gas v mixture with copper solution capable of absorbing CO, at a refri erated temperature. In testimony Where have hereunto set my hand.

JOSEPH G. DELY. 

